Fungicidal compositions of quinoneoxime-hydrazones



United States Patent FUNGICIDAL COMPOSITIONS OF QUINONE- OXIME-HYDRAZONES Ewald Urbschat, Koln-Mulheim, and Paul-Ernst Froliberger, Odenthal, Bezirk K0111, Germany, assignors to Farbenfabriken Bayer Aktiengesellschat't, Leverkusen, Germany, a corporation of Germany No Drawing. Application Februm 23, 1954, Serial No. 412,096

Claims priority, application Germany February 25, 1953 7 Claims. (Cl. 167-30) The present invention relates to useful improvements in fungicides; more particularly it is concerned with quinone oxime acyl hydrazones which are useful for rendering grain immune against attack by fungi.

Acyl azophenols are known to be highly eflicacious disinfectants against seed grain diseases.

In accordance with the invention it has been found that quinone oxime acyl hydrazones, which do not reach the efiicacy of the above mentioned compounds when applied in the combating of most seed grains diseases, have an extraordinary fungicidal activity against fungi causing germination diseases, for instance in leguminous plants, beets, maize, flax, cotton etc. infested by such fungi. The eflicacy of the quinone oxime acyl hydrazones is by far superior to that of the above acyl azophenols. Therefore the compounds of the invention are highly potent seed grain disinfectants.

The term quinone oxime acyl hydrazones as herein used is contemplated to denote compounds corresponding to the general formula in which R stands for a mononuclear or multinuclear quinoidal aromatic radical, R for hydrogen or an organic radical or, if n is a number greater than one, for any desired link; the radical R1 as well as the radical R may be substituted; R1 is attached to X, directly or through a hetero atom such as O, N, or S; X stands for one of the following groups:

ll ll lhl 0 0 and n is an integer.

These compounds are obtainable according to known processes, for instance by condensation of quinone monoximes or nitrosophenols with carboxylic acid hydrazides, thiocarboxylic acid hydrazides, sulphonic acid hydrazides, semicarbazides, thiosemicarbazides, or aminoguanidines.

Suitable quinone components according to the invention are for instance quinone monoxime, nitrosophenol, alkylnitrosophenols, halogenonitrosophenols, nitrosonaphthols and other hydroxynitroso compounds which are capable of reacting with the above hydrazides.

Examples of hydrazides which are useful for condensation with the quinone component are benzoic acid hydrazides, alkylbenzoic acid hydrazides, halogenobenzoic acid hydrazides, nitrobenzoic acid hydrazides, aminobenzoic acid hydrazide, dimethylaminobenzoic acid hydrazide, hydroxybenzoic acid hydrazide, alkoxybenzoic acid hydrazide, phenoxybenzoic acid hydrazide, formic acid hydrazide, acetic acid hydrazide, cyanoacetic acid hydrazide, propionic acid hydrazide, valeric acid hydrazide, lauric acid hydrazide, crotonic acid hydrazide, cinnamic acid hydrazide, hydroxybutyric acid hydrazide,

Patented Mar. 12, 1957 hydroxyisovaleric acid hydrazide, hydroxyacetic acid bydrazide, alkoxyacetic acid hydrazides, phenoxyacetic acid hydrazides, thioacetic acid hydrazide, methylthioacetic acid hydrazide, alkylcarbonic acid hydrazides, phenylcarbonic acid hydrazide, phenylacetic acid hydrazide, naphthoic acid hydrazide, naphthylacetic acid hydrazide, pyromucic acid hydrazide, carbohydrazide, thiocarbonic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide and succinic acid hydrazide.

Condensation products of quinone oximes or nitrosophenols with aminoacetic acid hydrazide, methylaminoacetic acid hydrazide, dimethylaminoacetic acid hydrazide, trimethylammoniumchloride-acctic acid hydrazide or pyridiniumchloride-acetic acid hydrazide, may be employed in the form of their salts, for instance as chlorides, nitrates, phosphates, dithiocnrbamates, thiocyanates, dinitrophenolates, or pentachlorophenolates.

The products obtainable from nitrosophenols and semicarbazide, phenylsemicarbazide, thiosemicarbazide, phenylthiosemicarbazide, dithiocarbazinic acid esters, aminoguanidine and benzoic sulfonic acid hydrazide are also suitable according to the invention.

The above named compounds are given only by way of illustration but it shall be understood that the scope of the invention shall by no means be restricted to the use of these compounds.

Germination diseases are already being controlled by means of metal-free substances such as tetramethylthiuram disulfide or 2,3-dichloro-naphthoquinone-l,4. Whereas these compounds must be applied in formulations containing at least 50% of active ingredient, quinone oxime acyl hydrazones, for instance quinone oxime benzoyl hydrazone, are effective in 10-15% formulations in the case of beets. In the latter case, the 2.5% formu lations of the hydrazone proves to be at least equivalent to a disinfectant containing 2.2% Hg as phenyl-Hg-acetate, provided that the same quantities are applied. The products of the invention are the first mercury-free compounds that reach the fungicidal activity of organic mercury compounds.

For the purpose of seed disinfection, the quinone oxime acyl hydrazones are applied in the usual manner either as such or after addition of the customary diluents. They may also be applied in admixture with other fungicides or insecticides, and they may contain substances preventing birds from picking up the seed grain, or products improving their solubility or dispersibility or otherwise favourably affecting their properties.

The solutions of the quinone oxirne acid hydrazones or their salts in suitable solvents may be used as seed disinfectants according to conventional methods.

The tests with polyeinbryonote sugar beets, which are described in the examples, were carried out with seed infected with root rot pathogens. The germination me dium was compost containing root rot soil fungi. The germination temperatures were maintained at l0-l5 C. These factors provided conditions that are considered most unfavourable for the development of the plants.

In the tests with leguminous plants, the infected seed (peas and beans) was disinfected in the usual manner and sown in compost containing fungi pathogenic to seedlings of leguminous plants, cultivation was carried out in the greenhouse at approx. 10 C. These conditions are extremely unfavorable to peas and especially to beans, because germination diseases are known to occur to a very large extent when the speed of germination is strongly delayed at low temperatures.

The invention is further illustrated by the following examples without being restricted thereto.

Example 1 A dry disinfectant containing 2.5% of quinone oxime benzoyl hydrazone in talcum was applied to polyembryonate sugar beet seed in an amount of 6 grams per kg. From 100 beet balls sown resulted 84 shooting-up spots from which 152 beet plants developed. During the next four weeks, only eight of these plants perished from root rot. Seed treated under entirely equal conditions including the beginning of the tests with a commercial dry disinfectant containing 2.2% of mercury showed 68 shooting-up spots from 100 balls sown, resulting in 134 beet plants; 64 plants thereof perished during the next four weeks. When untreated, the same seed resulted in 56 shooting-up spots which yielded 106 plants, 40 of which perished owing to root rot during the next four weeks.

Example 2 In another test carried out as described in the preceding example, application of the same disinfectant containing 2.5% of quinone oxime benzoyl hydrazone had the following result: shooting up spots with 170 plants were obtained from 100 beet balls. Only ten plants subsequently died off. After treatment of the seed with the Hg disinfectant, 62 shooting-up spots with 120 plants were obtained, 60 perishing. Untreated seed resulted in 46 shooting-up spots with 72 plants, 52 perishing.

In the same series of tests, the application of a disinfectant containing of quinone oxime benzoyl hydrazone resulted in 80 shooting-up spots with 172 plants all of which were healthy even after four weeks. A 30% formulation of the dry disinfectant containing the same active ingredient and applied in an equal amount did not show any depression of germination. This proves that the substance is well tolerated by the seed.

Example 3 Pea seed was treated with a dry disinfectant containing of quinone oxime benzoyl hydrazone in an amount of 2 grams per kg. and then cultivated as described above. After 24 days 100 peas had yielded 70 healthy plants. 45 healthy plants were obtained from seed treated with a commercial Hg-disinfectant, but only healthy plants were obtained from untreated seed.

Example 4 After a test period of 24 days, 100 beans treated with a dry disinfectant containing 10% of quinone oxime benzoyl hydrazone in an amount of 2 grams per kg. produced 92 healthy and two sick plants. In the same test, application of the commercial Hg-disinfectant resulted in 81 healthy and 8 sick plants. The untreated seed produced only 3 plants.

Example 5 Wheat seed was artificially infected in the usual manner with 5 grams of smut spores per kg. and subsequently treated with a dry disinfectant containing 5% of quinone oxime benzoyl hydrazone in an amount of 2 grams per kg. In the spore germination test carried out by the Gassner method, the untreated seed showed an almost complete germination of the spores, whereas the spore germination of the treated seed was sporadic only.

In the following examples:

The tests-the results of which are summarised in the tables below-were carried out in the greenhouse with polyembryomate sugar beet seed infected with Phona betae in compost infested with Pythium debaryanum. The temperatures during the tests varied between 10 and 20 C.

The compositions for use as dry disinfectants were extended with talcum.

Example 6 after 4 weeks amount number cone., in grams or the No. active substance percent per 1 kg. healthy number Hg of seed shootingol the up spots healthy after plants sowing 100 balls untreated 40 66 phenyl-Hg-acetato 2. 2 6 52 88 qulnona oxlme-onltro- 10 6 46 I04 benzoyl-hydmzone. qulnone oxtme-m-nl- 10 6 62 118 trobenzoyl-hydrazone. 5 qulnone oxime-p-nltro- 10 6 62 110 benzoyl-hydrazone. 6 do 15 6 68 134 7 qulnone oxlm e-o-hy- 15 6 56 100 droxybenzoyl hydrazone. quinone oxlme- 'chlo- 10 6 60 110 rohenznyl hy zone. -do 15 6 64 118 qulnone oxime24-dll0 6 66 130 ehlorobenzoylhydrazone. 11 do 15 6 54 122 Example 7 after 4 weeks amount number cone, in grams of the No. active substance percent per 1 kg. healthy number Hg of seed shootingof the up spots healthy alter plants sowing 100 balls untreated 49 74 pheuyI-Hg-acetate. 2. 2 6 72 123 qulnono oxlme eyano- 10 6 82 168 acetyl hydrazone. 4 do. 15 6 I82 5 qulnone oxlme acetyl- 1D 6 7D 18D hydrazone. 6 do 15 6 D0 196 Example 8 after 4 weeks amount number cone, in grams of the No. active substance percent per 1 kg. healthy number Hg of seed shootingof the up spots healthy alter plants sowing balls untreated 20 30 phcnylllg-acetate. 2. 2 6 32 66 qulnone oximv carbonic 5 6 50 acid ethylester-hydtazone. 4 do 15 6 48 86 5 qulnone oxlme-p-amino- 5 6 52 101 benzoyl-hydrazone. 6 2-methyl-quimme mt- 5 6 46 84 ime-benzoyl-hydrazone. -..d0 l5 6 40 74 3-[nethyl-qulnone ox- 5 6 40 I14 inie benzoyl-hydrazone. 9 do l5 6 46 92 10 quinone oxime- 5 6 44 92 formylydrazone 11 do 15 6 60 118 12..-" quinone oxlme ben- 5 6 34 El) zoyl-hydrazone sodium. 13 do 15 6 52 90 Example 9 alter 4 Weeks amount number cone. in grams of the No. active substance percent per 1 kg. healthy number Hg of seed shootingof the up spots healthy after plants sowing 100 balls 1 untreated 1 28 40 phenyl-Hg-aoetate 2. 2 6 4D 81 qulnone oxlme-car- 5 6 72 150 home sold methylestcr-hydrazone. 4 do 15 6 52 132 5 qulnone oxlme-car- 5 6 50 104 bonlc acid phenylester-hydrazone. do 15 6 62 130 qulnone oxlme pyro- 5 6 74 154 mucic acid hydrazone. -d 15 B 52 132 qulnone oxlrne car- 6 52 102 bonlc acid p-chlorophenyl-ester-hydrazone. 0 6 48 86 11"--. quinone oxlme me- 5 6 62 136 thoxy-acetlc acid hydrazone. 12 .d0 15 6 64 128 13 qninone oxlme 5 G 54 114 ethoxy-ecetlc acid hydrazone. 14 do 15 6 46 96 Example 10 after 4 weeks amount number cone., in grams of the No. active substance percent per 1 kg healthy number Hg of seed shootingof the up spots healthy after plants sowing 100 balls untreated 39 79 phenyl-Bg-acetate 2. 2 6 49 103 qulnone oxlme 5 6 02 138 hydroxyecetlo acid hydrazone.

Example 11 after 4 Weeks amount number cone, in grams of "the No. active substance percent per 1 kg. healthy number Hg of seed shootingof the up spots healthy aft er plants sowlng 100 balls 1 untreated 49 89 phenyl-Hg-acetate. 2.2 6 63 158 quinone oxlme meth- 5 6 66 176 lamlnoacetlc acid ydrazone-hydrochloride. 4 do 15 6 76 176 5 qulnone oxlme meth- 5 6 72 158 lamlnoacetic acid ydrazone. 6 dor 15 (5 74 198 7 quinone oxlme acetic 5 6 76 154 acid hydrazone-thiocyanate. 8 do 15 8 S0 204 9 quinone oxlme p-dl- 5 6 S4 172 methylamlnotenzoic acid hydrazone. 10 -.do l5 6 70 156 Example 12 efterweeks amount number cone, in grams of the No. active substance percent pcrlkg. healthy number Hg of seed shootingof the up spots healthy after plants 10 sowing 100 balls 1 untreated 38 58 2s phenyl-Hg-acetatem 2.2 6 50 95 qulnone oxlme phen- 5 6 47 95 15 ylthlosemiearbazone.

Example 13 after 4 weeks amount number 00110.. in grams or the No. active substance percent perlkg. healthy number Hg of seed shootingof the up spots healthy after plants sowing 100 balls 1 untreated 14 32 2 phenyl-I-Ig-aeetate m 2.2 6 34 M 3 quinone orlrne thio- 5 6 32 62 sernlcarbezone. 4 qulnoueoxime ernlno 15 6 3D 61 guanldyl hydrazonenitrate.

Example 14 afteMwoeks amount number cone, in grams of the No. active substance percent perlkg. healthy number Hg of seed shootingof the up spots healthy after plants sowing 100 balls untreated 49 74 phenyl-Hg-acetete 2.2 6 72 123 quinone oxime ben- 15 6 65 107 zene sultonlc hydrazone.

Example 15 aiter'lweeks amount number conc.. lngrams of the No. active substance percent perlkg. healthy number Hg of seed shootlngof the up spots healthy after plants sowin 100 balls 1 untreated 28 42 2 phenyl-Hg-acetate. 272 6 32 66 3 lobbmqulnoneoxlflle 15 6 30 55 benzoylhydrazone. 4 u-uaphthoqulnone ex- 15 6 30 61 lrne benzoyl-hydrazone.

In the following examples different seeds are treated with a composition of different quinonc oxime acylhydrazones in the form of a dry seed disinfectant formulation (with talcum).

Example I6.(Grain of mustard-seed) amount healthy cone., in grams plants No. active substance percent per 1 kg. from 100 Hg of seed sown seeds untreated 52 phenyl-Hg-acetate 2. 2 2 70 quinone oxime henzoyl hy- 2 76 drazone.

Example 1 7 .(Lupme-seed) amount healthy 00120., in grams plants No. active substance percent per 1 kg. from 100 Hg of seed sown seeds untreated 22 phenyl-Hg-acetate" 2. 2 2 28 quinone oxime benzoyl-hy- 5 2 50 drazone.

Example 18.-(Cucumber-seea') amount healthy cone, in grams plants No. active substance percent per] kg. from 100 Hg of seed sown seeds untreated l9 phenyl-Hg-a-cetnte 2.2 2 35 qulnone oxime benzoyl-hy- 5 2 55 drazone. 4 do 15 2 66 Example I9.-(Ctt0n-seed) amount 3 conc., in grams g mu No. active Substance percent per 1 kg. sown Hg Seed seeds after 4 weeks untreated 64 phenyl-Hg-acetate. 2. 2 6 78 quinone cyanoecetyl hydrn- 5 (i 74 zone. 4. d0 6 78 5. quinone oxime acetyl hydm- 5 6 88 zone. 6. do.... 10 6 74 7 quinoue tormyl hydraz0ne.- 5 6 82 8. 10 6 78 9... i5 6 78 10.. 0.01 88 11 quinone oxirne benzoyl 10 6 72 hydrazone. l2 d0 6 74 1 immersing for 16 hours,

Example 20.(Lmseed) amount $5 23 00110.. in grails s 6 No. active substance percent per 1 kg. mm

Hg of seed scrds after 4 weeks untreated 7 phenyl-Hg-acetatc 2. 2 2 80 quincne oxinte cyanoacctyl 5 2 77 hydrazone. 4 d0 10 2 82 5 qulnoneoxime acetyl-hydre- 5 2 82 zone. 0 .r quinone oxime formyl-hy 2 79 drazone. 7......" do h 20 2 78 8 sodium salt of quLnone 5 2 83 oxixne benzoyl-hydrazone. 9 do 20 2 81 10 qutnoue oximo benzoyl- 10 2 s? hydrazone. 11 20 2 81 Example 21.(Maize) Seeds of barley infected with Ustilago nuda are treated with a solution of an active quinone oxime acylhydrazone. After treatment the seeds are sown in the field.

average N 0. active substance mode of application and attack quantity in percent 1 untreated 6 2 lnetlioxyethyl- 1.75% Hg dry substance2g. to 3.6

Hg-sillcate L000 g. barley seed.

3 quinone oxime 16 hours swelling of 600 g. barley l. 5

ior myl-hydreseed in a solution of 50 zone. g. of quinone oxime lorrnylhydrazone in 1,000 g. of water.

47 eeee do in the same manner in a solution 0. 4

of 300 mg. of quinone oxlme form yihydrazone in 1,000 g. of water.

. sodium salt of 16 hours swelling offiClO g barley 1.5

quinone oxime seed in a solution of the sodium benzoyi-hydrasalt of quinone oxirne phenylzone. h ydrazone in 1,000 g. of water.

6 do in the ame manner in a solution I. 3

of 300 mg. of the sodium salt; of quinone oxime phenylhydrazone in [.000 g. of water.

Example 23 Seeds of wheat are contaminated with spores of T illetia tririci in an amount of 5 g. per 1 kg. of seed. After contamination the seed is treated with a dry seed dressing In this example the tests-the results of which are summarised in the table belowwere carried out in the greenhouse with polyembryomate sugar beet seed infected with Phone berae in compost infested with Pythium debnryanum.

benzoylor formyl-hydrazones as follows:

The seeds are treated with quinone oxiine after I weeks number cone, oithe No. active substance percent quantity healthy number Hg shooting- 01 the up spots healthy after plants sowing 100 balls 1 untreated 24 42 2 phenyl-Hg-acetate 2.2 6 to 1,000 (it; 1343 3 slurry-seed dressing of qui- 20 2g. +13 g. water" 50 128 none oxime beuzoyl-hydrazone with emulsifier and 70% caoline. 4 wet seed disinfectant of qui- 1 611100 kg 54 108 none oxizne benzoyl-hydraf zone in a solution of NauOOs-i-EOZ, NBISOQ. 5 like 5 [lL/llli] kgl oil 128 6...-.. wet seed dressing of qulnone 2.5 tiLjlUU kg til) 128 oxirne tormyl-hydrazone (80% NaHOOa). 7 like6 5 61,1100 kg 43 116 8.0- liquid seed dressing of 5% (lg/l kg 60 160 quinnne oxime benzoylhydrazone (2% NaOH, 1% Wetting agent). i

What we claim is:

l. A fungicidal composition containing as an active fungicidal substance a quinone-oxime-acylhydrazone having the following general formula:

(HO-N=R=N--NHx) R in which R is a quinone radical, R is a member selected from the group consisting of hydrogen and organic radicals, x is a radical chosen from the group consisting of 1 1 i) l NH and n is an integer not higher than 2, and a carrier.

2. A fungicidal composition containing as an active fungicidal substance a quinone-oxime-acylhydrazone having the following general formula:

in which at is a member selected from the group consisting of -o c c R is a member selected from the group consisting of hyin which x is a member selected from the group consisting of R is a member selected from the group consisting of hydrogen, alkyl amino-alkyl, oXi-alkyl, mercapto-alkyl, cyanoalkyl, aralltyl, and aryl radicals, and a carrier.

4. A fungicidal composition containing as an active fungicidal substance a quinone-oxime-acylhydrazone having the following general formula:

in which R is a member selected from the group con sisting of hydrogen, alkyl amino-allay], oxi-alkyl, mercaptoalkyl, cyano-alkyl, aralkyl, and aryl radicals, and a. carrier.

5. A fungicidal composition containing as an active fungicidal substance 21 quinone-oxime-acylhydrazone having the following general formula:

in which R is a member seelcted from the group consisting of hydrogen, alkyl amino-alkyl, oxi-alkyl, mercapto-alkyl, cyano-alkyl, aralkyl, and aryl radicals, and a carrier.

6. A fungicidal composition containing as an active fungicidal substance a quinone-oxime-acylhydraz0ne having the folowing general formula:

in which Z is a member selected from the group consist- 1ng of O, S and NH and R is a member selected from the group consisting of OR, OR being an alkyl radical having from i to 4 carbon atoms and phenyl radicals, and a carnor.

7. A fungicidal composition containing as an active fungicidal substance quinone-oxime benzoylhydrazone, and a carrier.

References Cited in the file of this patent UNITED STATES PATENTS 2,429,099 Ladd Oct. 14, 1947 

1. A FUNGICIDAL COMPOSITION CONTAINING AS AN ACTIVE FUNGICIDAL SUBSTANCE A QUNINON-OXIME-ACYLHYDRAZONE HAVING THE FOLLOWING GENERAL FORMULA: 